The mechanism of the oligomerization reaction of silica, the initial step of silica formation, has been studied by quantum chemical techniques. The solvent effect is included by using the COSMO model. The formation of various oligomers (from dimer to tetramer) was investigated. The calculations show that the anionic pathway is kinetically preferred over the neutral route. The first step in the anionic mechanism is the formation of the SiO-Si linkage between the reactants to form a five-coordinated silicon complex, which is an essential intermediate in the condensation reaction. The rate-limiting step is water removal leading to the oligomer product. The activation energies for dimer and trimer formation (similar to 80 kJ/mol) are significantly higher than those of the subsequent oligermerization. The activation energies for the ring closure reaction (similar to 100 kJ/mol) are even higher. The differences in activation energies can be related to the details in intra- and intermolecular hydrogen bonding of the oligomeric complexes.